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Hydrogen from PostConsumer Residues

S. Czernik, R. French, R. Evans, E. Chornet National Bioenergy Center


U.S. DOE Hydrogen and Fuel Cells Merit Review Meeting Berkeley, CA May 19-23, 2003

Goal of the Project


This work is one of three tasks in the Biomass to Hydrogen project. Goal: develop and demonstrate technology for producing hydrogen from biomass at $2.90/kg purified hydrogen by 2010. By 2015, be competitive with gasoline.

Objectives of the Task


Explore feasibility of producing hydrogen from lowcost, potentially high-hydrogen-yield renewable feedstocks that could complement biomass, increase flexibility and improve economics of Biomass to Hydrogen process. Can help overcome a barrier of high cost and availability of feedstock. Demonstrate efficiency of pyrolysis/reforming technology in application to readily available postconsumer wastes: plastics, trap grease, mixed biomass and synthetic polymers. Addresses the challenge of technology improvement.

Potential for Hydrogen


Plastics wastes: 15 Mt/year; potential for producing 6 Mt/year of hydrogen (energy equivalent 0.8x1018J/year) enough to fuel 15-20 million fuel cell vehicles
Requires development of collection programs and separation technologies. Target streams: manufacturing residues (textiles), MRF tailings.

Trap grease recovered: 6 kg/year/person - 1.5 Mt/year; potential for 0.5 Mt/year hydrogen.
Assuming that processing costs will be comparable to those for residual oil ($0.7/kg H2), trap grease presents a near-term market opportunity for the production of hydrogen.

Approach
Technology being developed for producing hydrogen from biomass:
Pyrolysis or partial oxidation of biomass, plastics, and other solid organic residues. Catalytic steam reforming of the resulting pyrolysis gases and vapors. Catalytic steam reforming of biomass-derived liquid streams (trap grease).

Opportunities to co-process different feedstocks.

Process Reactions
500-800C

Polymers

Monomers and other volatile compounds

CnHmOk + (n-k) H2O n CO + (m/2 +n-k) H2 n CO + n H2O n CO2 + n H2

800C, cat.

Project Timeline
Hydrogen from Post-Consumer Residues
FY02
Production of Hydrogen by Catalytic Steam Reforming of Trap Grease
Reforming tests using commercial catalyst Reforming tests using NREL fluidizable catalysts Feedstock clean up strategy and long-term catalyst performance demonstration Co-process trap grease with other biomass-derived liquids

Timeline
03 04 05 06 07 08 09

80% yield, 150 hours on stream, catalyst attrition losses. 80% yield, low attrition of catalyst 80% yield, low catalyst attrition, long-duration activity

Production of Hydrogen by Integrated Pyrolysis/Reforming of Plastics


Proof of Concept at Micro-Reactor/MBMS scale Bench-scale tests using integrated bubbling bed reactor system Bench-scale tests using plastic mixtures (gas clean up) Bench-scale co-processing of biomass and other feedstocks 80% yield from variety of feedstocks Completed

Production of Hydrogen from Different Feedstocks in Support of the Scale up Effort


Construction of bench-scale circulating fluid bed reformer Bubbling and circulating bed tests on flexible feedstocks

Milestones
1. Production of hydrogen from plastics by fluidized bed pyrolysis/reforming process; yield 80% of stoich. (34 g H2/100 g PP). September 2003. 2. Demonstrate efficiency of fluidisable, attrition resistant catalyst developed at NREL for trap grease reforming; 80% of the stoich. yield (28 g H2/100 g grease). September 2003.

Fluidized Bed Integrated Pyrolysis Reforming System

Process Conditions
Pyrolysis zone at 600 - 700C (Operated in both pyrolysis and POX mode) Steam flow: 240 g/h Feed rate: 60 g/h polypropylene Reforming zone at 850C Commercial nickel-based catalyst Molar (Steam/Carbon): 4.6 GC1HSV: 1600 h-1

Product Gas Composition


Pyrolysis/Reforming of Polypropylene
80 70 60 50

H2 CH4 650C 600C

15000

10000 ppm, vol. 5000 0


6.0 8.0 10.0

% vol.

40 30 20 10 0 0.0 2.0 4.0

CO2 CO C2H4
Time, h

Yield of Hydrogen
Pyrolysis/Reforming of Polypropylene
(stoich. yield: 42.9 g H2/100 g PP)

If followed by WGS
100 80

% stoich.

60 40 20 0 0 2 4

Actual 650C 600C

10

Time, h

Trap Grease
Collected from different sites in the U.S. by Pacific Biodiesel for DOE Biodiesel Program. Mixture of C16 and C18 free fatty acids and fats; Elemental analysis: C: 76.2%; H: 11.8%; O: 11.9%; N: 0.02%; S: 70 ppm; ash: 0.1%; Process conditions: Temperature: 850C, NREL fluidisable catalyst Grease feed rate: 42 g/h, steam flow: 240 g/h S/C: 5, GC1HSV: 970 h-1

Trap Grease Product Gas Composition


80 70 60 50 H2

% vol.

40 30 20 10 0 0 50 100 T im e , h
5.0

CO C O2 150 200

4.0

% vol.

3.0 CH4 2.0

1.0

C2H4 C6H6

0.0 0 20 40 60 80 100 120 140 160 180 Time , h

Yield of Hydrogen
Reforming Trap Grease
(Stoich. yield of H2: 35 g/100 g grease)
100

Reforming + WGS

80

60

Reforming

40

20

0 0 20 40 60 80 100 120 140 160 180

Time, h

Other Accomplishments
Publications:
Chornet, E. and Czernik, S., Renewable fuels: Harnessing hydrogen, Nature 2002, 418, 928-929. Czernik, S., French, R., Feik, C., Chornet, E.; Hydrogen by Catalytic Steam Reforming of Liquid Byproducts from Biomass Thermoconversion Processes, I&EC Research 2002, 41, 4209-4215.

Record of Invention filed in U.S. DOE.

Collaboration:
Interface Research Corp., National Diesel Board, American Apparel Manufacturers Association.

Future Work
Complete milestones for FY 2003. Demonstrate pyrolysis/reforming process for complex feedstocks (textiles, mixed plastics) using commercial and NREL developed catalysts. Demonstrate production of hydrogen by coprocessing renewable (solid and liquid biomass and wastes) and fossil (natural gas) feedstocks.